Insect-controlling compositions and method for controlling insects thereby



Patented Jan. 28, 1947 INSECT-CONTROLLING COMPOSITIONS AND METHOD FOR CONTROLLING IN- SEOTS THEREBY Murray Senkus, Ten-o Estate, 11111., aalignor to Commercial Solvents Corporation, Terre Haute, Ind., a corporation of Maryland No Drawing. Application August 4. 1945, Serial 809 082 1 This invention relates to new and useiul insect-controlling compositions and more particularly to compositions containing along with a solid or liquid carrier a S-amino-L3-disubstituted hexahydropyrimidine compound having the following structural formula:

CH1 RIN/ N-R H: I H:

c Nfia \R wherein R may be either hydrogen, alkyl, aryl or hydroxymethyl, and R may be alkyl, aryl, aralkyl, Z-hydroxyalkyl, dialkylaminoalkyl or 3,5-dioxa cyclohexyl.

I have found that the new compositions of my invention are useful not only as insecticides and as toxic compositions for controlling and killing insects, but have also high insect-repellency characteristics which adapt them for use in this capacity, and especially for use in mothprooflng rugs. fabrics and the like, and for rendering various surfaces insect-repellent.

The fi-aminohexahydropyrimidines illustrated above may be prepared by catalytic hydrogenation in the liquid phase under pressure, of the corresponding 5-nitrohexahydropyrimidines, as described in my copending application Serial No. 547,282, filed July 29, 1944. The 5-nitrohexahydropyrimidines used as starting materials in the preparation 01' theamino compounds may be prepared by reacting a suitable primary amine and formaldehyde with a, nitrohydrocarbon having the nitro group attached to a primary carbon atom, in the mole ratio of approximately three moles of formaldehyde to two moles of primary amine to one mole of nitrohydrocarbon, as described in my copending application Serial No. 547,281 filedJuly 29, 1944.

The proportions of the substituted 5-aminohexahydropyrmidines, which may be used in the compositions according to my invention may vary widely depending upon the composition or carrier with which they are associated and upon the nature of the insect pest to be controlled, as well as on the particular substituted 5-aminohexahydropyrimidine employed. Quantities up to about may be used, although usually much smaller quantities, in the range of about 1% to 10% will usually be suificient.

The insect controlling compositions of my invention comprise one Or more oi the substituted 5-aminohexahydropyrimidines mixed with a suitable carrier or vehicle. Any oi the vehicles or solvents commonly employed in insecticidal sprays and in which the compounds may be dissolved or emulsified may be used in preparing the insect controlling compositions of my inventions, such as kerosene. Ultrasene," alcohols, and other solvents, and these compositions may be made up as solutions or emulsions as appears appropriate or suitable dusts may be impregnated therewith.

The compositions of my invention have wide applicability in controlling insect pests, being valuable, not only as insecticides but also as repellents for flies, moths and the like, as brought out above and these characteristics are more fully illustrated by the repellency, mothproofing and toxicity tests described below:

EXAMPLE I RIPILLENCY ro Ho'csnrrrs The substituted fi-aminohexahydropyrimidine compounds listed below were made up in alcoholic solution, using 10% concentration of the aminohexahydropyrimidine. The solutions were sprayed on separate blotter strips of 1 inch 'b 3 inches area, with five inch holes in each of the blotter-s and these blotter strips were placed Table I nm-m-nonlll nmrmlmc! mars WITH HOUSE ms mat repellency at hour intervals tested Compound EXAMPLE II after squeezing out the excess liquid were hung Fl re ellenc tests ere run in the same manin an made atmophere to dry for at least ner is t at desiribedYn Example 1, except that The chm! were Placed in individual th 5-am1no-hexahydropyflmid1neg were made 25 containers with 5 carpet beetle larvae for feedup in 50% solutions in alcohol. The fly repeli s test and resu ts obs ve wee y for three lencies at the hourly intervals noted. are listed wee W e t e w no feeding of t in the table below: beetles, or where the ieeding was negligible the Table II BAIT-IN-HOLE BEPELLENCY TESTS WITH HOUSE FLIES Per cent repellency at intervals noted, hours Compound EXAMPLE m mothprooflng is indicated as good. Where rm there was some feeding; the results are described Mo mo G 50 as doubtful, and where feeding was equal to Pieces 01' wool mohair cloth were dipped in althat on an untreated piece of wool the results coholic solutions of various o-aminohexahydroare indicated as zero. These resultsare tabupyrimidines at the concentrations indicated and lated below.

Table III MOTHPROOFING 5% concentration 1% concentration Compound 1 week 2 weeks 8 weeks 1 week 2 weeks 3 weeks 5-alnino-1,3-bis l-methylhe tyl)-5-methyl-hexahydropyrimidlne Gaol..- Gr gd.

5-8mili10-i1 iilx-lbis 2,2-dimcthyl-3-dimethyl-amlnopropyl -5-lnethylhexahydrodo. Good.

pyrm c.

b-antilijnig-hll-bifll-methyl-t, li-dioxacyclo-hexyl) IS-methylhexshydropyrldo. Do.

m e. t

5-amino'l,3diisopl'opy1-6-hydroxymethyl-hexahydropyrimidine.. Poor.

5-amino-l,3-bis(2-ethylhoxyl)-6-ethyl-hexahydropyri ldine..- Good.

ll-smino-l,3-dihexahydrobenzyl-5-methy1hexailydropyrimldin Do.

5-am.no-l,3-di-p-tolyl-B-methylhexa-hydropyrlmidine. 5-am mo-l,3-bis(1-methyihe tyD-Iwthylhexahydropyrim 5-am.no-l,3-dibenzyl-5-met ylhexa-hydropyrlmidine 6-a1zrino-L3-bls(l-methyi 3,5-dioxa-cyclohexyl)-b-isopropylhexahydropyrimie. 5-amin0-l,3-dibenzyl-5- ropylhexahydropyrlmldine 5-amino-1,3-bls(2-ethy exyl)-5-methylhexahydropyrlmldine 6-amino-l,3-dibensyl-5-(2-ethylhexyl)-hexahygiropyrimidlne 5-amino-l,3-dioctadecyi-fi-ethylhexahydropyrlmidine 5-amino-l,3-dilsopxopyl-5-(24thylhexyl)-huahydropyrimidlne o-amino-l,a-dimethyl-b-phenylhexahydropyrimldlne EXAMPLE IV Fur Sm! Toxrcerrr Tssrs The toxic eflects of my new insect controlling compositions were evaluated by means .of a

standard technique employed in testing materials as fly spray toxicants. In carrying out these tests, twenty flies were confined in each of several spherical screen cages, and each cage was revolved in a spray of the test solution until about 1.2 cc. of solution had been applied.

Table IV Pal; cl'sgitflklll a y Compound s ray in tmeene" B-amino-l 3-bis(l-methylhe'ptyl)-6-methyl-hexahydropy imidine e2. 7 o-admlno-lfi-diisopropyl-b-methylhexahydropyriml- 38 2 no B-amino-l,3-bis(2,2-dimethyl-3-dimethylaminopropyl)- B-methylhexahydropynmidine 40.2 o-an i i no-lfi-blsfl-ethy hexyl)-5-ethylhexahydropyri- 13 in nu fi-amino-l.3-dihexahydrobenzyl--methyihexahydropyrimidine 67.2 o-amino-l ,S-di-p-tolyl-S-methylhexahgdropyrimidine 83 o-amino-l.3-bis(l-mothylheptyl)-5-et ylhexahydropyrimidine 63 fi-amino-l,S-dibenzyl-5methylhexahydropyrimidino 86 fi-amino -l,3-bis (l -methyl-3,5-dioxacyclohexyl) -5-isopropylhexahydropyrimidine 6-amlno-l,3-bis(l-methyl- ,5-dioxacyclohexyl)-5-propylhexahydropyrlmidine 12 fi-amino-l ,Irdibenzyl-5-propylhexahydropyrimidino 89 G-amino-1,3-bis(2-ethylhexyl) -5-methylhexahydropyrimidine 71 5-amino-1,3-dibenzyl-5-(2-ethylhexyl)-hexahydropyrimidlne 70 o-amlno-l (idlisopropyl-5-(2-ethylhexy1)-hexahydropyrimidine 42 5-amino-1,3-dimethy1-5-phenylhexahydropyrimidine l7 EXANIPLE V 5-amino-l,3-bis(l-methylheptyl) 5 methyl- EXAMPLE VI 5-amino-1,3-bis(l-methylheptyl) 5 methylhexahydropyrimidine made up to a solution in alcohol was sprayedon various surfaces and the fly repellency tested as follows:

Drops of paraifln were placed on each sample, and on each of the paraffin spots were placed malt extract to serve as fly food. Each treated sample and a control were placed in hemispherical wire cages along with twenty flies. Duplicates of each test sample were hung outdoors and indoors, and the feeding of the flies noted upon the several samples. After feeding, results were noted, the flies were removed, .the samples allowed to age, and at various intervals as indicated in Table V below, twenty flies were again placed in each cage, and their feeding noted. The results are illustrated in the table below.

6 Table v REPELLENCY OF 50% SOLUTIONS OF 5-AMINO-L3- E HYLHEXAHY DRO- BIS(1-METHYLHEPTYL) 5 -M T PYRIMIDINE 0N VARIOUS SURFACES No. of iiiee feeding at Barbee location i 8 days 7 days 11 days Indoon..... 0 6 l5 MM {Outdoomm c a ll Painted wood. Indoors. '13 18 White paint Outdoors.... 13 I) Unpeinted wood.--.. doors"... 0 0 3 0utdoore... 16 i4 Untreated. mutt-01..-. 12-18 15-18' Another group of tests similarly run with the same solution gave the following results indicated in percent repellency based on a standard of 8 flies normally feeding.

Table VI Percent repellency et- Burieoe Location 7 days 14 days 21 days Indoors-.. 100 100 100 p grim-"- {8% g 00. Lacquered scream... {gg 1,63

' 00H. minim {Outdoor-a..- 100 100 100 G1", {Indoor-s. 100 100 87.5 Outdoors.... 100 37. 6 12. 5

The N-substituted 5-aminohexahydropyrimias a solution or an emulsion, particularly since most of the compounds are themselves liquids. However, it may be desirable in some cases to apply the toxic and repellent compositions in the form of dusts. and in such cases suitable solid carriers such as pyrophyllite, talc or the like may be impregnated with the desired quantity of the fi-amino-hexahydropyrimidine compound, and the dust applied to the surface to be controlled.

The 5-aminohexahydropyrimidines may be used with a suitable carrier, either singly or mixed, or in combination with other insecticides or insect controlling. compositions, and are particularly useful in admixture with certain insecticides of the type which are toxic but not repellent to insects, for example in combination with insecticides of the 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane type and 0! the aliphatic thiocyanate type to yield compositions highly eflective in both repellency and toxicity to various insect pyrimidine and a carrier therefor.

2,415,047. 7 5. A method for rendering suriscss insect rehexahydropyrimidine and a liquid carrier pellent which comprises treotin: ssid surfaces therefor.

with a composition comprising a. 5-amino-1,3- '7. The method of claim .6, wherein the 5- disubstituted-hexshydropyrimidine and a. carrier amino-1,3-disubstituted-hexahydropyrimidine is therefor. 5 5-amino-1,3-bis(1-methy1hepty1) -5-methy1hexas. Amethod m moth-proofing mums which hydropyrimidine. comprises impreznatina said isbric with A composition comprising a S-amino-LS-disubstitutedmummy snmms. 

